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| United States Patent |
5,314,949
|
|
Kozakura
, et al.
|
May 24, 1994
|
Polycarbonate resin composition
Abstract
A polycarbonate resin composition comprising 1 to 99% by weight of a
branched polycarbonate having a branched nucleus structure derived from a
branching agent represented by the general formula:
##STR1##
wherein R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
and R.sup.1 to R.sup.6 are hydrogen atoms, alkyl groups having 1 to 5
carbon atoms or halogen atoms, respectively, and 99 to 1% by weight of a
thermoplastic polyester resin. The polycarbonate resin composition is
excellent in fluidability, solvent resistance and moldability.
| Inventors:
|
Kozakura; Shiro (Ichihara, JP);
Kuze; Shigeki (Ichihara, JP);
Tanaka; Kenji (Ichihara, JP)
|
| Assignee:
|
Idemitsu Petrochemical Co., Ltd. (Tokyo, JP)
|
| Appl. No.:
|
028366 |
| Filed:
|
March 9, 1993 |
Foreign Application Priority Data
| Jan 24, 1991[JP] | 3-022664 |
| Mar 13, 1992[JP] | 4-055199 |
| Current U.S. Class: |
525/67; 525/439 |
| Intern'l Class: |
C08L 069/00; C08L 067/02 |
| Field of Search: |
525/67,439
|
References Cited
U.S. Patent Documents
| 2866771 | Dec., 1958 | Sellers et al.
| |
| 2971939 | Feb., 1961 | Baer et al.
| |
| 3544514 | Dec., 1970 | Schnell | 528/204.
|
| 4001184 | Jan., 1977 | Scott.
| |
| 4415723 | Nov., 1983 | Hedges et al. | 528/204.
|
| 4436879 | Mar., 1984 | Miller | 525/439.
|
| 4515925 | May., 1985 | Kleiner | 525/439.
|
| 4652602 | Mar., 1987 | Liu | 524/449.
|
| 4710534 | Dec., 1987 | Liu | 525/67.
|
| 4788251 | Nov., 1988 | Brown | 525/148.
|
| 4866123 | Sep., 1989 | Wittmann | 525/67.
|
| 5008330 | Apr., 1991 | Laughner | 525/67.
|
| 5068285 | Nov., 1991 | Laughner | 525/67.
|
| 5087663 | Jan., 1992 | Laughner | 525/67.
|
| 5087665 | Feb., 1992 | Chung | 525/133.
|
| 5104964 | Apr., 1992 | Kuze | 528/202.
|
| Foreign Patent Documents |
| 675110 | Jul., 1966 | BE.
| |
| 1238164 | Jun., 1988 | CA.
| |
| 0106225 | Apr., 1984 | EP.
| |
| 0120394 | Oct., 1984 | EP.
| |
| 0131196 | Jan., 1985 | EP.
| |
| 0400478 | Dec., 1990 | EP.
| |
| 44-17149 | Jul., 1969 | JP.
| |
| 59-45318 | Mar., 1984 | JP.
| |
| 60-11733 | Mar., 1985 | JP.
| |
| 3-182524 | Aug., 1991 | JP.
| |
Primary Examiner: Buttner; David
Attorney, Agent or Firm: Frishauf, Holtz, Goodman & Woodward
Parent Case Text
REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part application of application Ser.
No. 07/820,206 filed Jan. 13, 1992 now abandoned.
Claims
What is claimed is:
1. A polycarbonate resin composition consisting essentially of
(A) 30 to 98% by weight of a branched polycarbonate having a branched
nucleus structure derived from a branching agent represented by the
formula (I):
##STR6##
wherein R is a hydrogen atom or an alkyl group having 1 to 5 carbon
atoms, and R.sup.1 to R.sup.6 are hydrogen atoms, alkyl groups having 1 to
5 carbon atoms or halogen atoms, respectively, the branched polycarbonate
having a viscosity average molecular weight of 15,000 to 40,000, and an
acetone-soluble matter of not more than 3.5% by weight, and
(B) 70 to 2% by weight of polybutylene terephthalate resin.
2. The polycarbonate resin composition according to claim 1 wherein the
branched polycarbonate is represented by the formula:
##STR7##
wherein m, n, and o are integers, respectively, and PC indicates a
polycarbonate moiety.
3. The polycarbonate resin composition according to claim 2 wherein the
polycarbonate is made from bisphenol A.
4. The polycarbonate resin composition according to claim 2 wherein the
polycarbonate has a repeating unit represented by the formula:
##STR8##
5. The polycarbonate resin composition according to claim 1 wherein the
branching agent is 1,1,1-tris(4-hydroxyphenyl)ethane.
6. A polycarbonate resin composition consisting essentially of (A) 40 to
94% by weight of a branched polycarbonate having a branched nucleus
structure derived from a branching agent represented by the formula (I):
##STR9##
wherein R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
and R.sup.1 and R.sup.6 are hydrogen atoms, alkyl groups having 1 to 5
carbon atoms or halogen atoms, respectively,
the branched polycarbonate having a viscosity average molecular weight of
15,000 to 40,000, and an acetone-soluble matter of not more than 3.5% by
weight, and (B) 5 to 59% by weight of a polybutylene terephthalate resin
and 1 to 50% by weight of a rubber elastomer as a component (C), the total
amount of the component (A), the component (B) and the component (C) being
100% by weight.
7. The polycarbonate resin composition according to claim 6, wherein
component (A) is in an amount of 45 to 80% by weight, component (B) is in
an amount of 10 to 40% by weight and component (C) is in an amount of 3 to
30% by weight, the total amount of the component (A), the component (B)
and the component (C) being 100% by weight.
8. The polycarbonate resin composition according to claim 7, wherein the
branching agent is 1,1,1-tris(4-hydroxyphenyl)ethane.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a polycarbonate resin composition, and
more particularly to a polycarbonate resin which has an improved
fluidability and solvent resistance in addition to the mechanical
properties of conventional polycarbonate resin compositions, and is
excellent in moldability, particularly in blow moldability.
2. Description of the Related Arts
Processes for production of polycarbonate using phloroglucine or
trimellitic acid as a branching agent have heretofore been known, as
disclosed in for example, Japanese Patent Publication Nos. 17149/1969, and
11733/1985. Use of these branching agents, however, suffers from a
disadvantage in that a trace amount of unreacted matter is apt to cause
coloring.
In Japanese Patent Application Laid-Open No. 45318/1984,
1,1,1-tris(4-hydroxyphenyl)ethans is proposed to be used as a branching
agent. However, the specification of U.S. Pat. No. 4,415,723 discloses
that the polymer obtained by using this branching agent is colored to pals
yellowish green in Comparative Example A, and suggests the use of a
branching agent such as 1,1,2-tris(4-hydroxyphanyl)ethans and
1,1,2-tris(4-hydroxyphenyl)propane. Yet the process disclosed in the above
U.S. Pat. No. 4,415,723 cannot completely solve the problems of coloring.
It is known that when a polycarbonate is branched for blow molding, its
impact resistance decreases. Accordingly, development of a branched
polycarbonate with high impact resistance had been required.
The present inventors' group had investigated from such points of view, and
succeeded in solving the problem of hue to develop a branched
polycarbonate suitable for blow molding which have acetone-soluble matter
of not more than 3.5% by weight and an improved impact-strength (Japanese
Patent Application Laid-open No. 182524/1991).
SUMMARY OF THE INVENTION
As a result of present inventors' intensive investigations to further
improve moldability and solvent resistance of the above-mentioned branched
polycarbonate, it has been found that a polycarbonate resin composition
having the desired properties can be obtained by means of blending a
prescribed amount of thermoplastic polyester resin with a specified
polycarbonate, without imparing the mechanical properties of conventional
polycarbonate resin composition.
The present invention has been accomplished based on the above findings.
That is, the present invention provides a polycarbonate resin composition
comprising (A) 1 to 99% by weight of a branched polycarbonate having a
branched nucleus structure derived from a branching agent represented by
the general formula (I):
##STR2##
wherein R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
and R.sup.1 to R.sup.6 are hydrogen atoms, alkyl groups having 1 to 5
carbon atoms or halogen atoms, respectively, a viscosity average molecular
weight of 15,000 to 40,000, and an acetone soluble matter of not more than
3.5% by weight, and (B) 99 to 1% by weight of a thermoplastic polyester
resin.
The polycarbonate resin composition may comprise 40 to 94% by weight of the
component (A) and 5 to 59% by weight of the component (B) and further
comprise 1 to 50% of a rubber elastomer as a component (C).
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The branched polycarbonate of component (A) of the present invention has a
branched nucleus structure derived from a branching agent represented by
the general formula (I):
##STR3##
wherein R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms,
such as methyl group, ethyl group, n-propyl group, n-butyl group, and
n-pentyl group; and R.sup.1 to R.sup.6 are hydrogen atoms, alkyl groups
having 1 to 5 carbon atoms (e.g., methyl group, ethyl group, n-propyl
group, n-butyl group, and n-pentyl group) or halogen atoms (e.g., chlorine
atom, bromine atom, and fluorine atom).
The embodiments of the branching agent of the general formula (I) include
1,1,1-tris(4-hydroxyphenyl)methane;
1,1,1-tris(4-hydroxyphenyl)ethane;
1,1,1-tris(4-hydroxyphenyl)propane;
1,1,1-tris(2-methyl-4-hydroxyphenyl)methane;
1,1,1-tris(2-methyl-4-hydroxyphenyl)ethane;
1,1,1-tris(3-methyl-4-hydroxyphenyl)methane;
1,1,1-tris(3-methyl-4-hydroxyphenyl)ethane;
1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)methane;
1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane;
1,1,1-tris(3-chloro-4-hydroxyphenyl)methane;
1,1,1-tris(3-chloro-4-hydroxyphenyl)ethane;
1,1,1-tris(3,5-dichloro-4-hydroxyphenyl)methane;
1,1,1-tris(3,5-dichloro-4-hydroxyphenyl)ethane;
1,1,1-tris(3-bromo-4-hydroxyphenyl)methane;
1,1,1-tris(3-bromo-4-hydroxyphenyl)ethane;
1,1,1-tris(3,5-dibromo-4-hydroxyphenyl)methane; and
1,1,1-tris(3,5-dibromo-4-hydroxyphenyl)ethane.
The above branched polycarbonate posesses the branched nucleus structure
derived from a branching agent represented by the above-mentioned general
formula (I), and specifically represented by the following formula:
##STR4##
wherein m, n and o are integers, and PC represents a polycarbonate moiety.
The polycarbonate represents, when bisphenol A is used as starting material
component, for instance, a repeating unit of the following formula:
##STR5##
The branched polycarbonate of Component (A) has a specified branched
nucleus structure as described above, and a viscosity average molecular
weight of 15,000 to 40,000. If the viscosity average molecular weight is
less than 15,000, impact resistance of the resulting composition is low,
while if it is in excess of 40,000, moldability of the composition results
to be poor.
In the above branched polycarbonate, the portion of acetone soluble matter
is preferably not more than 3.5% by weight. If the portion of
acetone-soluble matter exceeds 3.5% by weight, impact resistance of the
composition becomes to be markedly low. The acetone-soluble matter therein
refers to a component extracted from the objective polycarbonate by
Soxhlet extraction using acetone as a solvent.
Above-mentioned branched polycarbonate can be produced according to various
processes. For example, the branched polycarbonate can be efficiently
produced by a process disclosed in Japanese Patent Application Laid-Open
No. 182524/1991, which comprises reacting (i) a polycarbonate oligomer
derived from aromatic dihydric phenols, a branching agent represented by
the general formula (I), and phosgene, (ii) aromatic dihydric phenols, and
(iii) a terminal stopper while stirring in such a way that a reaction
mixture containing them is under a turbulent flow condition, and adding
aqueous alkali solution at the point where the viscosity of the reaction
mixture rises and, at the same time, reacting the reaction mixture under a
laminar flow condition.
The branched polycarbonate can also be produced by reacting (i) a
polycarbonate oligomer derived from aromatic dihydric phenols and
phosgene, (ii) aromatic dihydric phenols, (iii) a branching agent
represented by the general formula (I), and (iv) a terminal stopper while
stirring so that a reaction mixture containing them is under a turbulent
flow condition, and adding aqueous alkali solution at the point where the
viscosity of the reaction mixture increases and, at the same time,
reacting the reaction mixture under a laminar flow condition.
As a thermoplastic polyester resin as Component (B) of the present
invention, various ones can be used. As the preferred examples, a
polyester resin obtained by polymerization of a bifunctional carboxylic
acid component and an alkylene glycol component is suggested.
Examples of bifunctional carboxylic acid components and alkylene glycol
components are as follows. Bifunctional carboxylic acid components include
aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid,
and naphthalene dicarboxylic acid. Among these dicarboxylic acids,
terephthalic acid is preferred. Other bifunctional carboxylic acid
components can also be used in combination so long as the effect of the
present invention is not impaired. Typical examples of the other
bifucntional carboxylic acid are aliphatic dicarboxylic acids such as
oxalic acid, malonic acid, adipic acid, suberic acid, azelaic acid,
sebacic acid, and decanedicarboxylic acid, and ester forming derivatives
thereof. The proportion of the dicarboxylic acid component other than
aromatic dicarboxylic acids is preferably 20% or less of the total
dicaroboxylic acids.
The alkylene glycol component is not critical, but specifically aliphatic
diols having 2 to 15 carbon atoms such as ethylene glycol,
propylene-1,2-glycol, propylene-1,3-glycol, butylene-1,4-glycol,
butylene-2,3-glycol, hexane-1,6-diol, octane-1,8-diol, neopentyl glycol,
and decane-1,10-diol can be used. Among these diols, ethylene glycol and
butylene glycol are preferred.
As the polyester resins, particularly preferred ones are polyethylene
terephthalate and polybutylene terephthalate.
The thermoplastic polyester resin as component (B) can be prepared by a
conventional method in the presence or absence of a polycondensation
catalyst containing titanium, germanium, antimony or the like. For
example, polyethylene terephthalate can be prepared by the reaction
comprising two steps. At the first step, terephthalic acid and ethylene
glycol are esterified, or a lower alkyl ester of terephthalic acid such as
dimethyl terephthalate and ethylene glycol are transesterified to obtain a
glycol ester of terephthalic acid and/or a low polymer thereof. At the
second step, that is, polymerization reaction step, the glycol ester
and/or a low polymer thereof are further polymerized to give a polymer
having a high polymerization degree.
In the composition of the present invention, the proportion of the branched
polycarbonate as Component (A) is 1 to 99% by weight, preferably 30 to 98%
by weight, to the total amount of Components (A) and (B). The
thermoplastic polyester resin as Component (B) is incorporated in a
proportion of 99 to 1% by weight, preferably 70 to 2% by weight. If the
proportion of the branched polycarbonate exceeds 99% by weight, the
resulting composition is not improved sufficiently in fluidability and
solvent resistance. On the other hand, if the proportion of the
above-mentioned branched polycarbonate is less than 1% by weight, the
mechanical strength and the moldability of the composition are lowered,
and no effect by branching the polycarbonate is obtained.
Various compounds can be used as a rubber elastomer of the component (C) .
Examples of the rubber elastomer include (1) those prepared by
polymerizing one or more vinyl-based monomers in the presence of a rubber
polymer obtained from monomers mainly comprising either or both of an
alkyl acrylate and an alkyl methacrylate. The alkyl acrylate and the alkyl
methacrylate each preferably has 2 to 10 carbon atoms, specific examples
of which include an ethyl acrylate, a butyl acrylate, a 2-ethylhexyl
acrylate, a non-octyl methacrylate and the like.
Examples of the rubber polymer made from monomers mainly comprising these
alkyl acrylates include polymers obtained by reacting 70% by weight or
more of said alkyl acrylates with 30% by weight or less of copolymerizable
other vinyl-based monomers such as methyl methacrylate, acrylonitrile,
vinyl acetate, and styrene. Polyfunctional monomers such as divinyl
benzene, ethylene dimethacrylate, triallylcyanurate and triallyl
isocyanurate may be added in a proper amount as a crosslinking agent in
this reaction.
Examples of the vinyl-based monomer which is reacted in the presence of
said rubber polymer include an aromatic vinyl compound such as styrene and
a-methyl styrene, an acrylic ester such as methyl acrylate and ethyl
acrylate, a methacrylic ester such as methyl methacrylate and ethyl
methacrylate and the like.
These monomers may be used singly or two or more in mixtures. The monomers
may also be copolymerized with other vinyl-based monomers, for example, a
vinyl cyanide compound such as acrylonitrile and methacrylonitrile, a
vinyl ester compound such as vinyl acetate and vinyl propionate and the
like.
The polymerization can be conducted according to various methods such as
bulk polymerization, suspension polymerization and emulsion
polymerization. Particularly emulsion polymerization is suitable.
The so obtained rubber elastomer contains preferably 20% by weight or more
of said rubber component. Specific examples of this rubber elastomer
include a MAS resin elastomer, for example, a graft copolymer combining 60
to 80% by weight of a n-butyl acrylate with a styrene or a methyl
methacrylate.
Said MAS resin elastomer is commercially available, for example as "KM-330"
(tradename, supplied by Rhome & Haas Co.), as "METABLEN W 529" (tradename,
supplied by Mitsubishi Rayon Co., Ltd.) and the like.
Other examples of said rubber elastomer are (2) those prepared by
polymerizing one or more of vinyl-based monomers with a copolymer which is
obtained by copolymerizing either or both of an alkyl acrylate and an
alkyl methacrylate and a polyfunctional monomer having a conjugated
diene-type double bond. The alkyl acrylate and the alkyl methacrylate are
the same as exemplified in (1) above. Examples of the polyfunctional
monomer having the conjugated diene type double bond are a conjugated
diene compound such as butadiene and isoprene and a compound having a
conjugated diene type double bond and further a non-conjugated double bond
per molecule. They are for example, 1-methyl-2-vinyl-4,6-heptadiene-1-ol;
7-methyl-3-methylene-1,6-octadiene; 1,3,7-octatriene; and the like.
In said process wherein either or both of the alkyl acrylate and alkyl
methacrylate are copolymerized with the polyfunctional monomer having the
conjugated diene type double bond, a vinyl-based monomer may be added, if
necessary, including an aromatic vinyl compound such as a-methyl styrene,
a vinyl cyanide compound such as acrylonitrile and methacrylonitrile, a
vinyl ester compound such as vinyl acetate and vinyl propionate, a vinyl
ether compound such as methylvinyl ether and a halogenated vinyl compound
such as vinyl chloride. Furthermore, a crosslinking agent such as ethylene
dimethacrylate and divinyl benzene may as well be added.
The so obtained copolymers are polymerized with the vinyl-based monomers
which are same as exemplified in (1) above. These monomers may be used
singly or two or more in mixtures. The polymerization can be conducted
according to various methods such as bulk polymerization, suspension
polymerization and emulsion polymerization. Particularly emulsion
polymerization is suitable.
Preferred among these rubber elastomers is a graft copolymer obtained as
follows: an alkyl(meth)acrylate such as n-butyl acrylate, 2-ethylhexyl
acrylate or methyl methacrylate, a butadiene and further a small amount of
a crosslinking agent such as ethylene dimethacrylate or divinyl benzene
are copolymerized according to a conventional method; to the resultant
latex, vinyl-based monomers such as styrene, acrylonitrile,
methacrylonitrile or vinyl chloride are added as the graft component
monomer and the mixture is subjected to graft polymerization according to
a conventional method.
Another preferred rubber elastomer is a graft copolymer obtained as
follows: said alkyl (meth)acrylate and a compound having a conjugated
diene type double bond and further a non-conjugated double bond per
molecule are copolymerized according to a conventional method, to the
resultant latex said vinyl-based monomers are added as the graft component
monomer and the mixture is subjected to graft polymerization according to
a conventional method. This graft polymerization is conducted either in a
single step process or in a process consisting of a plurality of steps
dealing with the graft component monomers one by one.
Specific examples of these rubber elastomers are MABS resin elastomers
including a graft copolymer wherein an octyl acrylate and a butadiene are
copolymerized at a ratio of 7:3, to the resultant rubber latex styrene and
a methyl methacrylate are added and the mixture is subjected to graft
polymerization.
Still other examples of the rubber elastomer includes those obtained by
copolymerizing two or more of compounds selected from the group consisting
of a methacrylic ester monomer, a vinyl cyanide monomer and an aromatic
vinyl monomer in the presence of a rubber.
Various rubbers can be used herein. Specifically, they are a diene rubber
or a diene rubber mixture, for example, a butadiene rubber (BR), an
isoprene rubber (IR), a chloroprene rubber (CR), a piperylene rubber, a
styrene-butadiene copolymer rubber, a styrene-butadiene block copolymer
rubber, an acrylonitrile-butadiene copolymer rubber (NBR) and further an
ethylene-propylene rubber (EPR), a terpolymer wherein an ethylene and a
small amount of a diene are copolymerized (EPT), an isobutylene-isoprene
rubber (IIR), an ethylene-vinyl acetate rubber, a polyethylene chloride
rubber, an epichlorohydrin rubber and the like. Of them, the butadiene
rubber (BR) and the styrene-butadiene rubber (SBR) are particularly
suitable.
Furthermore, various compounds can be used as the methacrylic ester
monomer, examples of which include a methyl methacrylate, an ethyl
methacrylate, a propyl methacrylate, an isopropyl methacrylate, a butyl
methacrylate and the like. Of them, the methyl methacrylate is
particularly suitable.
Furthermore, examples of the vinyl cyanide monomer include an
acrylonitrile, a methacrylonitrile and the like.
Moreover, specific examples of the aromatic vinyl monomer include a
styrene, an a-methyl styrene, an o-methyl styrene, a m-methyl styrene, a
p-methyl styrene, a dimethyl styrene, a chlorostyrene and the like.
Other than those mentioned above, rubber elastomers for use in the present
invention include a thermoplastic resin obtained by copolymerizing two or
more compounds selected from the group consisting of those such
methacrylic ester monomers, vinyl cyanide monomers and aromatic vinyl
monomers according to a known method such as solution polymerization, bulk
polymerization, suspension polymerization, bulk-suspension polymerization
and emulsion polymerization. Particularly, a thermoplastic resin having a
high rubber content is preferably manufactured according to the emulsion
graft polymerization. Specifically, a methacrylic ester monomer and an
aromatic vinyl monomer are polymerized with a polybutadiene-based latex
according to the emulsion graft polymerization and the resultant
polybutadiene-based copolymer latex is coagulated with an inorganic acid
or an inorganic salt such as aluminum sulfate to obtain the desired
product.
Preferred among those obtained as described above is a thermoplastic resin
prepared by copolymerizing a styrene-methyl methacrylate or a
styrene-acrylonitrile in the presence of a butadiene copolymer containing
30% by weight or more of a polybutadiene or a butadiene. Meanwhile, the
above styrene compounds may be those in which a part or all of the styrene
is substituted with an .alpha.-methyl styrene. Preferred specific examples
of those styrene compounds include a methyl methacrylate-butadiene-styrene
resin (MBS resin) , an acrylonitrile-butadiene-styrene resin (ABS resin)
and the like.
The present invention provides a polycarbonate resin composition comprising
the abovementioned components (A), (B) and (C) . The components (A) , (B)
and (C) are mixed at a ratio of 40 to 94% by weight, preferably 45 to 80%
by weight of (A), 5 to 59% by weight, preferably 10 to 40% by weight of
(B) and 1 to 50% by weight, preferably 3 to 30% by weight of (C).
In the polycarbonate resin composition of the present invention, various
inorganic fillers, additives or other synthetic resins, elastomers and the
like can, if necessary, blended so long as the purpose of the present
invention is not impaired.
Inorganic fillers blended in order to improve the mechanical strength, the
durability, or the increase in quantity of the polycarbonate resin
composition include glass fibers (GF), glass beads, glass flakes, carbon
black, calcium sulfate, calcium carbonate, calcium silicate, titanium
oxide, alumina, silica, asbestos, talc, clay, mica, and quartz powder.
The aforementioned additives include anti-oxidizing agents of hindered
phenol type, phosphorus type such as phosphite and phosphate, and amine
type; UV absorbers such as benzotriazoles, and benzophenones; external
lubricating agents such as aliphatic carboxylates, and paraffines;
conventional flame-retardants; mold release agents: antistatic agents:
colorants and the like.
As the hindered phenol type anti-oxidizing agents, BHT
(2,6-di-tert-butyl-p-cresol), Irganox 1076 and Irganox 1010 (trade name,
produced by CIBA-GEIGY CO. ), Ethyl 330 (trade name, produced by ETHYL
CO.), Sumilizer GM (trade name, produced by SUMITOMO CHEMICAL CO., LTD. )
and the like are preferably used.
Examples of the other synthetic resins are polyethylene, polypropylene,
polystyrene, acrylonitrile-styrene (AS) resin,
acrylonitrile-butadiene-styrene (ABS) resin, polymethyl methacrylate, and
polycarbonates other than the above-mentioned branched polycarbonate.
Examples of elastomers are isobutylene-isoprene rubber, styrene-butadiene
rubber, ethylene-propylene rubber, acrylic elastomer and the like.
The polycarbonate resin composition of the present invention can be
prepared by blending the above-mentioned components and kneading them.
Blending and kneading can be conducted by a conventional method with the
use of a ribbon blender, a Henschel mixer, a Bunbury mixer, a drum
tumbler, a single screw extruder, a twin screw extruder, a co-kneader, a
multiple screw extruder or the like. The Kneading is appropriately
conducted at a heating temperature usually in the range of 250.degree. to
300.degree. C.
The polycarbonate resin composition thus obtained can be molded by various
conventional molding methods such as injection molding, hollow molding,
extrusion molding, compression molding, calender molding, and rotary
molding to prepare molded products such as a bumper and other parts for
automobiles, molded products for home electrical appliances, etc. The
polycarbonate resin composition is suited particularly for blow molding
and extrusion molding, and is excellent in vacuum moldability, hollow
moldability, and heat bending moldability in the form of sheet or film.
As described above, according to the present invention, a polycarbonate
resin composition excellent in fluidability and solvent resistance, and
also in moldability, while posessing the mechanical properties of the
original polycarbonate can be obtained. The above-mentioned polycarbonate
is particularly suitable for blow molding. Accordingly, blow molding
products made from the polycarbonate resin composition of the present
invention has a markedly improved mechanical properties and solvent
resistance, compared with the conventional ones. Therefore, the
polycarbonate resin composition of the present invention is effectively
utilized for various molding products (e.g., industrial materials for
automobiles, home electric appliances, and office automation appliances),
particularly as the material for blow molding.
The present invention will be explained in greater detail with reference to
the following examples and comparative examples.
REFERENCE EXAMPLE
(1) Synthesis of Polycarbonate Oligomer A
60 kg of bisphenol A was dissolved in 400 L (L=liter) of a 5% aqueous
sodium hydroxide solution to prepare an aqueous sodium hydroxide solution
of bisphenol A.
Subsequently, the aqueous sodium hydroxide solution of bisphenol A
maintained at room temperature was introduced into a tubular reactor with
an inner diameter of 10 mm and tube length of 10 m through an orifice
plate at a flow rate of 138 L /hr, and methylene chloride was introduced
therein at a flow rate of 69 L /hr, and phosgene was blown thereinto in
parallel at a flow rate of 10.7 kg/hr to continuously react them for 3
hours. The tubular reactor used herein was a double tube, and the
discharge temperature of the reaction solution was maintained at
25.degree. C. by passing cooling water in the jacket section.
The discharged liquid (the reaction solution) was adjusted to pH 10 to 11.
The reaction solution thus obtained was allowed to stand, and thus the
aqueous layer was separated and removed to obtain 220 L of the methylene
chloride layer. Further, 170 L of methylene chloride was added to the
methylene chloride layer, and the resulting mixture was thoroughly
stirred. The product thus obtained was used as the polycarbonate oligomer
A (concentration: 317 g/ L). The degree of polymerization of the
polycarbonate oligomer thus obtained was 3 to 4.
(2) Synthesis of Polycarbonate Oligomer B
60 kg of bisphenol A and 0.58 kg of 1,1,1-tris(4hydroxyphenyl)ethane were
dissolved in 400 L of a 54 aqueous sodium hydroxide solution to prepare an
aqueous sodium hydroxide solution.
Thereafter, in the same manner as in (1) above, a polycarbonate oligomer
(Polycarbonate Oligomer B) with a concentration of 321 g/ L was obtained.
Preparation Example 1 (Preparation of Polycarbonate)
3.39 L of methylene chloride was added to 5.61 L of Polycarbonate Oligomer
B to prepare Solution I.
Separately, 173.4 g of sodium hydroxide and 482.9 g of bisphenol A were
dissolved in 2.9 L of water to prepare Solution II.
The above Solution I and Solution II were mixed, 0.856 g of triethylamine
as catalyst and 37.6 g of p-tert-butylphenol as a terminal stopper were
added thereto, and the mixture was stirred in a turbulent flow condition
for 10 minutes at 600 rpm.
Thereafter, 167 ml of an aqueous sodium hydroxide solution (concentration:
48% by weight) was added, and the resulting mixture was reacted while
stirring under a laminar flow condition for 60 minutes at 200 rpm.
After the reaction was completed, 5 L of water and 5 L of methylene
chloride were added, and the mixture was separated into a methylene
chloride layer and an aqueous layer. The methylene chloride layer was
alkali-washed with a 0.01N aqueous sodium hydroxide solution, and further
acid-washed with 0.1N hydrochloric acid.
Then, by washing with water, methylene chloride was removed to obtain
polycarbonate as a polymer in flake form. The acetone-soluble matter of
the flake-form polymer obtained was measured by Soxhlet extraction over 8
hours. The viscosity average molecular weight of the resulting
polycarbonate was 2.7.times.10.sup.4. The polycarbonate thus obtained is
referred to as A-1.
Preparation Example 2 (Preparation of Polycarbonate)
To 5.68 L of Polycarbonate Oligomer A, 3.32 L of methylene chloride was
added to prepare Solution III.
Solution III and Solution II used in Preparation Example 1 were mixed,
0.856 g of triethylamine as a catalyst, 37.6 g of p-tert-butylphenol as a
terminal stopper and 15.0 g of 1,1,1-tris(4-hydroxyphenyl)ethane as a
branching agent were added thereto, and the mixture were stirred under a
turbulent flow condition for 10 minutes at 600 rpm.
Then, 167 ml of an aqueous sodium hydroxide solution (concentration: 48% by
weight) was added thereto, and the reaction was conducted by stirring
under a laminar flow condition for 60 minutes at 200 rpm.
When the reaction was completed, 5 L of water and 5 L of methylene chloride
were added thereto, and a methylene chloride layer and an aqueous layer
were separated. The methylene chloride layer was alkali-washed with a
0.01N aqueous sodium hydroxide solution, and then acid-washed with 0.01N
hydrochloric acid.
Then, by washing with water, the methylene chloride was removed away, and a
polymer in flake, that is, polycarbonate was obtained. The viscosity
average molecular weight of the resulting polycarbonate was
2.7.times.10.sup.4. This polycarbonate is referred to as A-2.
Preparation Example 3 (Preparation of Polycarbonate)
The procedure of Preparation Example 1 was repeated except that 53.2 g of
p-cumylphenol was used in place of 37.6 g of p-tert-butylphenol. The
viscosity average molecular weight of the resulting polycarbonate was
2.7.times.10.sup.4. This polycarbonate is referred to as A-3.
Preparation Example 4 (Preparation of Polycarbonate)
The procedure of Preparation Example 1 was repeated except that 45.5 g of
p-tert-butylphenol was used. The viscosity average molecular weight of the
resulting polycarbonate was 2.1.times.10.sup.4. This polycarbonate is
referred to as A-4.
Examples 1 to 11 and Comparative Examples 1 to 5
Each prescirbed amount of polycarbonate, thermoplastic polyester resin and
other additives was dried, and chip blended, then supplied to an extruder
to be kneaded at 270.degree. C., and pelletized. Further, the resulting
pellet was dried at 120.degree. C. for 6 hours, and injection-molded at a
die temperature of 80.degree. C. and a molding temperature of 270.degree.
C. to obtain a test piece.
The pellet was measured on melting properties (flow value, MIR, swell
ratio, and melting intensity), and the test piece was measured on tensile
strength and solvent resistance. The results are shown in Table 1-1 to
Table 1-4.
TABLE 1-1
______________________________________
Thermoplastic
Polycarbonate Polyester Resin
Ratio by Weight Ratio by Weight
Kind (wt %) Kind (wt %)
______________________________________
Example 1
A-1 90 PET*.sup.2
10
Example 2
A-2 90 PET*.sup.2
10
Example 3
A-3 90 PET*.sup.2
10
Example 4
A-1 70 PET*.sup.2
30
Example 5
A-1 50 PET*.sup.2
50
Example 6
A-1 30 PET*.sup.2
70
Example 7
A-3 30 PET*.sup.2
70
Example 8
A-1 70 PBT*.sup.3
30
Example 9
A-1 30 PBT*.sup.3
70
Example 10
A-4 90 PET*.sup.2
10
Example 11
A-1 95 PET*.sup.2
5
______________________________________
*.sup.1 Toughlon A2700 (polycarbonate produced from bisphenol A)
manufactured by Idemitsu Petrochemical Co., Ltd.
*.sup.2 Dianite MA523 (polyethylene terephthalate, intrinsic viscosity:
0.73 dl/g) manufactured by Mitsubishi Rayon Co., Ltd.
*.sup.3 Dulanex 2002 (polybutylene terephthalate, intrinsic viscosity:
1.06 dl/g), manufactured by Polyplastic Co., Ltd.
TABLE 1-2
__________________________________________________________________________
Result of Evaluation
Tensile
Strength Solvent
Flow Value Swell
Melt
(kg/cm.sup.2)
Resistance
(ml/sec)
MIR Ratio
Tension (g)
__________________________________________________________________________
Example 1
630 0.4 3.8 .times. 10.sup.-2
78 2.52
6.5
Example 2
630 0.4 3.8 .times. 10.sup.-2
78 2.53
6.5
Example 3
630 0.4 3.8 .times. 10.sup.-2
77 2.50
6.4
Example 4
620 0.5 4.4 .times. 10.sup.-2
66 1.65
4.2
Example 5
600 0.6 6.5 .times. 10.sup.-2
64 1.62
3.9
Example 6
580 0.7 8.9 .times. 10.sup.-2
64 1.48
3.2
Example 7
580 0.7 8.8 .times. 10.sup.-2
65 1.48
3.3
Example 8
630 0.5 3.2 .times. 10.sup.-2
75 1.38
4.3
Example 9
630 0.7 8.3 .times. 10.sup.-2
68 1.39
2.8
Example 10
630 0.4 8.2 .times. 10.sup.-2
79 2.52
4.8
Example 11
630 0.4 3.6 .times. 10.sup.-2
82 2.54
6.8
__________________________________________________________________________
TABLE 1-3
______________________________________
Thermoplastic
Polycarbonate Polyester Resin
Ratio by Weight Ratio by Weight
Kind (wt %) Kind (wt %)
______________________________________
Compara-
A-1 100 -- --
tive
Example 1
Compara-
B-1 100 -- --
Example 2
Compara-
B-1 70 PET 30
tive
Example 3
Compara-
B-1 70 PBT 30
tive
Example 4
Compara-
.sup. B-2*.sup.4
90 PBT 10
tive
Example 5
______________________________________
*.sup.4 Toughlon A2200 (polycarbonate produced from bisphenol A)
manufactured by Idemitsu Petrochemical Co., Ltd.
TABLE 1-4
__________________________________________________________________________
Result of Evaluation
Tensile
Strength
Solvent
Flow Value Swell
Melt
(kg/cm.sup.2)
Resistance
(ml/sec)
MIR Ratio
Tension (g)
__________________________________________________________________________
Comparative
630 0.2 2.5 .times. 10.sup.-2
75 2.75
6.9
Example 1
Comparative
630 0.2 2.2 .times. 10.sup.-2
20 1.13
0.8
Example 2
Comparative
610 0.5 4.1 .times. 10.sup.-2
30 1.18
1.5
Example 3
Comparative
620 0.5 1.8 .times. 10.sup.-2
32 1.20
1.3
Example 4
Comparative
630 0.4 8.2 .times. 10.sup.-2
25 1.12
0.8
Example 5
__________________________________________________________________________
Conditions of measuring melt properties, tensile strength, and solvent
resistance are as follows.
1) Flow Value Measured according to JIS K-7210.
2) MIR (Index for blow molding. Desired value is 50 or higher.) Melt index
ratio (MI.sub.11 kg /Mi.sub.325 g). Measured at 280.degree. C.
3) Swell ratio (indication of blow molding and the like. Desired value is
1.2 or higher.)
Value obtained by dividing a cross-sectional area of a strand extruded when
a load of 11 kg is applied to a molten resin in measurement of melt index,
by-a cross-sectional area of an orifice.
4) Melt Tension (Indication of blow molding and the like. Desired value is
2 (g) or higher.) Tension of strand resulted at a tensile rate of 9.42
re/min., Orifice: L/D=8/21 was measured at 280.degree. C.
5) Tensile Strength (kg/cm.sup.2) Measured according to JIS K-7113.
6) Solvent Resistance
Determined by critical strain in ratio by volume, in a solvent (ratio of
composition: toluene/isooctane=40/60), according to the 1/4 oval method
described in Nakatsuji et al. "Shikizai" vol. 39, page 455 (1966).
Examples 12 to 23
A polycarbonate and a thermoplastic polyester resin were dried at
120.degree. C. for 6 hours. These two dried materials, a green rubber
elastomer and other additives each in a prescribed amount were subjected
to dryblending according to the mixing composition shown in Table 1-5. The
resultant mixture was fed to an extruder, kneaded at 270.degree. C. and
pelletized. The so obtained pellets were dried at 120.degree. C. for 6
hours and then subjected to injection under the conditions of a die
temperature of 80.degree. C. and a molding temperature of 270.degree. C.
to obtain test pieces.
The pellets were measured for the melt properties (the flow value, the
swell ratio and the melt tension), while the test pieces were examined
relative to the tensile strength, the Izod impact strength and the solvent
resistance. The results thereof are given in Table 1-6.
TABLE 1-5
______________________________________
Mixing Composition (wt. %)
PC PET Rubber Elastomer
Mixed Mixed Mixed
Kind amount Kind amount
Kind amount
______________________________________
Example 12
A-1 70 PET 25 G-1 5
Example 13
A-2 70 PET 25 G-1 5
Example 14
A-3 70 PET 25 G-1 5
Example 15
A-4 70 PET 25 G-1 5
Example 16
A-1 50 PET 45 G-1 5
Example 17
A-1 60 PET 25 G-1 15
Example 18
A-1 70 PET 25 G-1 5
Example 19
A-1 60 PET 25 G-1 15
Example 20
A-1 70 PET 25 G-2 5
Example 21
A-1 60 PET 25 G-2 15
Example 22
A-1 70 PBT 25 G-2 5
EXample 23
A-1 45 PBT 35 G-2 20
______________________________________
TABLE 1-6
______________________________________
Physical properties
Tensile
Izod impact Critical
strength
strength*.sup.1
strain
kg/m.sup.2
23.degree. C.
-30.degree. C.
%
______________________________________
Example 12
600 90 20 0.5
Example 13
600 90 20 0.5
Example 14
600 90 20 0.5
Example 15
600 90 20 0.5
Example 16
550 80 15 0.6
Example 17
530 70 30 0.6
Example 18
650 85 18 0.6
Example 19
580 68 25 0.7
Example 20
580 85 35 0.5
Example 21
480 68 50 0.6
Example 22
620 80 30 0.6
Example 23
530 65 48 0.8
______________________________________
Physical properties
Flow value Melt
ml/sec Swell ratio
tension g
______________________________________
Example 12
4.5 .times. 10.sup.-2
1.65 4.0
Example 13
4.5 .times. 10.sup.-2
1.65 4.0
Example 14
4.5 .times. 10.sup.-2
1.66 4.1
Example 15
12 .times. 10.sup.-2
1.64 3.0
Example 16
6.8 .times. 10.sup.-2
1.58 3.8
Example 17
5.0 .times. 10.sup.-2
1.40 3.7
Example 18
3.5 .times. 10.sup.-2
1.35 4.2
Example 19
4.0 .times. 10.sup.-2
1.30 3.8
Example 20
4.8 .times. 10.sup.-2
1.70 4.2
Example 21
5.5 .times. 10.sup.-2
1.44 3.9
Example 22
3.8 .times. 10.sup.-2
1.38 4.4
Example 23
5.0 .times. 10.sup.-2
1.33 3.6
______________________________________
Furthermore, the melt properties, the tensile strength, the Izod impact
strength and the solvent resistance were determined under the following
conditions:
1) Flow value
Measured according to JIS K-7210.
2) Swell ratio (an indication of blow molding; and preferably a value of
1.2 or higher)
Determined by dividing a cross-sectional area of a strand extruded under
the following conditions by a cross-sectional area of an orifice with the
use of & capillary rheometer.
Extruding Conditions
Capillary L/D 20, D 1 mm .phi.
Temperature 280.degree. C.
Shear rate 243 cm.sup.-1
3) Melt tension (an indication of blow molding and the like; preferably 2
(g) or more)
The tension was developed on a strand under the conditions of a stress rate
of 9.42 m/min and an orifice of L/D=8/21. The so developed tension was
measured at 280.degree. C.
4) Tensile strength
Measured according to JIS K-7113.
5) Izod impact strength
1/8 in notched. Measured according to JIS K-7110.
6) Solvent resistance
The critical strain (the minimum strain capable of developing cracks) was
determined with the use of a solvent (toluene/isooctane=40/60) according
to the 1/4 oval method.
Furthermore the following materials were used in the examples and the
comparative examples:
(B-1): A conventional polycarbonate resin known as "TOUGHLON A2700"
(supplied by Idemitau Petrochemical Co., Ltd.)
(PET): A polyethylene terephthalate known as "DIANITE MA523" (supplied by
Mitsubishi Rayon Co., Ltd.)
(PBT): A polybutylene terephthalate as "DULANEX 2002" (supplied by
Polyplastic Co., Ltd.)
(G-1): A rubber-like elastomer MAS as "PARALOID KM330" (supplied by Rhome &
Haas Co.)
(G-2): A rubber-like elastomer MBS as "METABLEN C223" (supplied by
Mitsabishi Rayon Co. Ltd.)
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